Process of producing aldehyde esters



Patented Sept. y9, 1952 2.610,29afi rRocEss 0F PRODUCING ALDEHYDE i Es'rERs i NewA Jersey" v 'Ns litiasis. lpigucafmipstsllnr la; mit;

Serial No. 132,799

5 claims. (ci. 26o-:483i

This invention relates-"to the preparation `of aldehyde esters.` More partlcularl'yitliis' inven tion` is concerned with an improvedmethod of producing lsuch aldehydeestrsirom thereaction of unsaturatedl estcrsf` with carbon monoiklde'and 5 hydrogen.` Ther-present inventinlconstitutes a particularly useful method of producing compounds suchas ganima' foifmyl' ethyl butyrate and the' aldehyde estersiof succinieacid.

The aldehyde esters of the class described are useful compounds `partic'zularly as intermediates. That irihe aldhyd. esters, may be` reducea i@ fafmwdroxv commands whichuaaysluarl@ in the. preparationfnea? @Westera lldflacionesi Similarly, the] aldellyde esters`f inay1be;` Vused l `to form amines. Or the al'del'iyde`v estersrinay Vbe oxidized to form acid esters of utility in the preparation of plastici'zers, linear polyesters, polyamides and thelike. 1t, is therefore apparentthat the; providing of aaimprovd method capable 0i reasonably. `large-iscale `operationfor producing such` acid esters represents a highly desirable result. t.

We have discovered thatthe aldehyde esters fof the class referred to may be produced by reacting unsaturated esters? with Ycarbo`1'i monoxid saturated esters-exemp1meagfpy alkyl @femmes 5 and-the various"'acrylate esters.

In accordance -witli` the bro'aderfaspects of our invention; tlieunsaturated ester, f such as Aethyl used: likewise, certain hydri'ara es may be used but are considered` non-equivalent to the butanol diluent first mentior'edl Tlieuse of a diluent for the catalyst y is preferred for the am @habia taie ptosszwhsaaslihlfnts- .not usedthcre. aapraeilway baseleeiivs'ascfptca 0f lh? unsftul'atd L .@Selln :Al-1e. ll? Sll ofv the catalyst. thereby causing catalyst deactif lysts are principally `c use of jan" ester; of' ali` unsaturated acid. carbon rnonoxide1`hydrcgen`. and a suitablecatalyst; De'- tails w'ill'jnoyy'be s et forthcncerning; eac'liA of the aforementioned items.V @Wepre'fer rto use` a cobalt `catalyst incarrying out the prsent process, althoughotlier carbonyl-forming metals,` or mixtures thereof with the cobalt catalyst, may be employed. One cobalt-containing catalyst which may be used is a commercially obtainable materiai known as `JHa'rsiiaw' 5421 such .catafjm'priss @cessait sumiso contain thong cemeteries These.; grments aredeposited on af carrier. sic'h ,aseselgulin in a. sfilata/@0 rasoi `The"surcef Qfxcblt lust menpioped'istypical of thetype o fgz'njaterialt t maybe usedi"` fqrnig the catalyst employ the. presea# went catarsi maar M 1- @Midas 0f maar? @bali @r1 Silc gel, meenam'. #fafa ys Soluble catalysts catalyst alone we prefer to employ the catalyst dissolved or suspended in a suitable medium and the medium. it is to be understood that isoprolikewise be used. ,Y

panol and the other 2-6 carbonialcoholsfinayf In further regard to thel detail of suspending or solvent medium for catalysts, next to the hydroxy type of medium we prefer-*theY Carbonylj type of diluent exemplified by methyl ethyl ke-f' U e preferably a lower aliphatic alcohol medium..- if

While butanol is frequently referred to herein as l0 reduced pressure.. to give 61 grams of glutaric residue comprised largely of the dehydrated aldol 4condensation product of the aldehyde ester.

The aldehyde ester was oxidized with air to form the half acid ester. In addition -to '14 grams of monoethyl glutaric acidfesterg'B. Pio 134-138" C.4 grams of ethyl butyratewas also obtained which indicates the presence of a small amount "of isomeric alpha formyl ethyl butyrate in the principal prdl1ct,gamma formyl ethyl butyrate. The acid ester was hydrolyzed and distilled at acid M.'P. 95-j96 .2f"C. Glutaronitrile and penta- `methylenefdi`amine were also prepared to further prove'thatithe gamma formyl ethyl butyrate tone, acetone, and also the various aldehydes. i

Also, as already mentioned, ethers may be used exemplied by the common ether, di-ethyl ether, and likewise, the other ethers 'such `as 'propyl ether and lower aliphatic ethers Vmay be used. As the last type of diluent; mention 'is made of the hydrocarbons, b ut such type of diluent vis not preferred. As a matter of fact, the rstmentioned 4diluents are suiciently superior to the other diluents that general we shall prefer tovuse a hydroxy or carbonyl diluent, although for thepurposes of complete disclosure herein examples areset forth describingour process as ,carried out when ethers and Aother compounds are used'as diluents. Y

Commercial sources of carbon monoxide and hydrogen may be used, lsuch as ingredients jde-i rivedfrom the water gas reaction. For best ope eration these gases will .beltreiated if they'contain impurities, to removecomponents suchwas sulfur and the like and vparticularly to remove oxygen and preferably also to remove carbon dioxide.'

Any suitable source of esters of unsaturated acids may be employedin this invention. For example, 'the process functions very satisfactorily with ethyl crotonate and :similar estersA of unsaturated acids. Further details' concerning the various esters which maybe reacted in accordance with the present invention will beobtained as the description proceeds; In the preferred embodiment, the reaction is. carried out under a temperature between 130 and1160 C. and under pressurel betweenA 1600 pounds per square inchand 3500 p. s. i. These and other details will be further apparent from a consideration of the following examples which lare set forth to illustrate the present invention.v

Example I Twenty grams of 'a cobalt-thoria-magnesiacatalyst precipitated on kieselguhr and v'l0 per cent reduced was suspended in 158 grams of ethyl crotonate. The slurry was charged to van 800 ml. stainless steel rocking autoclave and heated to 140 C. Carbon monoxide and hy-'A drogen in a 1/1 ratio were pressed in at pressures up to 3500 p. s. i.V `Anexothermicreaction took place and the temperature of the autoclave reached 165 C. with pressures between 1200-3500 p. s. i. The reaction rate'j was 1.1 gram. mol/hour.' At the `completion of the reaction the contents of the autoclave were' blown off, ltered and weighed. The reaction product weighed 184 grams. Distillation gave 17'y grams of unchanged ethyl crotonate, 105 ,gramsjof the aldehyde ester, B. Pn 8590 Cyand 60 grams oi was the principal oxonation product of ethyl cro- Example II Y Example v-The reaction was` carried-j foutafs lrin E'xaiylnple II with only -200 cc. off*diethylfether'Vdiluent; The rate of reaction was6,f1gramniples .per hour. 186` gramsof, gamma formyljrethyl butylrate was obtained:V n AExample IV- u u u Four hundredl ml. of benzene' was substituted for the diethyl ether ofvExarmp'leIIlfThefrate of reaction was v6.7 gram'inolsV per hour."V 175 grams"` of gammaV formyl ethyl rbutyrate was ob-l tained. Y I 1- d Y Y 'Example l Forty grams of cobalt-thoria-rnagnesia cata; lyst was Suspended-1111400, m1# .Qfrethyl, acrylate dilutedV with 400 ml.oi `Y diethyl ether .`'1fhe s uspension was lcharged to aV-:roclcerautoclave and reacted with carbon monoxide andfhydrogen-at 14o-152 c.l and Vicoofznoo Vp.y -,s,,i. @reaction rate of 5.4 gram mols` per hourwasobtained The reaction was blown down, ltered and .distilled. '87 .gramsr of alpha v lformylqethyllprof; pionate B. P. 484-527`-C. at 10 millimeters and 2 03. grams of beta formyl ethyl propionate Wasch; tained B. P 8 1-84" C. at 10 millimeters. f

' Vltrcantple VIf Forty grams of cobalt thcria.-m'agriesiaY cata-- lyst, 58%'reduc'e`d, was suspended amixture of 400 ml. of diethyl maleatefdil ledfwith 400 ml. of dioxanel The suspension was charged a rocker autoclave andfreacted. with V.carbon monoxide. and hydrogen "ati" Q11Q`1583 C." and. 22001-3500 p.V s. i. V blown off, ltered`,jand distilledfji.Inladditiiif to" unchanged diethyl Inaleate, 317 'grams-0f alpha' formyl diethyl succinate, B; P. i "imi 1Mb-11.9"A C. was obtained; 'Example VIII. vTwenty ygrams,v ofcobalt-silicafcatalyst', 40%1ieo haltreduced-was 'suspendedinl200- grams of ethyl-sabia .diluted with- Qamt -ofr'pdrethyl ether;-

The suspension Awas charged to a. rocker TheA reaction. 'product =was autoclave and. .reacted Wtheerbon monoxide and hlr f est 27m-350er. s.; i; .and 13e-1,54; ion of: lth reaction, product save 141 of"xisorngerioV diforinyl `ethyl sorbates, 35i-16v? v Q,

l Estesi@ mi] W Two' hundred-r strains of' Aethyl 1 crotonate was mixedl withx grams' of cobalt `carbonyl butanol in 2 00 inl.H of butanol` and `reacted with carbon Example X Twenty grams of solid catalyst containing 30.1% cobalt, 1.7% thoria, 2.1% magnesia, and 66 grams of supercel was suspended in 400 grams of ethyl crotonate and charged to a one liter autoclave. Carbon monoxide and hydrogen were pressed in at Z500-3500 p. s. i. and 13D-110 C`. The rate of oxonation was 4.3 gram mols/hour. Distillation of the product gave a 42% yield oi gamma formyl ethyl butyrate.

The above reaction conditions were varied by the addition of 60 grams of water. The rate of oxonation was 13.6 gram mals/hour and a 70.2% yield of gamma `.Eormyl ethyl butyrate was obtained.

Eample XI 400 grams of the ethyl ester of 2-ethy1 crotonic acid were reacted as in Example X with no diluent or water present. Ihe rate of oxonation was 3.6 gram moles per hour and a 46% yield of gamma formyl alpha ethyl ethyl butyrate was obtained.

The oxonation was repeated using A grams of Water. A reaction rate of 11.2 gram mole/hour was observed and a 64% yield of gamma formyl, alpha ethyl ethyl butyrate was obtained.

Example XII Ten grams of cobalt carbonyl was dissolved in 300 grams of butyl crotonate and oxonated at 140i10 C. and 2200-3000 p. S. i. A reaction rate of 5.2 gram mols per hour was observed and a 37% yield of gamma formyl butyl butyrate was obtained.

The above oxonation was repeated using 2-00 grams of butanol as a diluent and charging the butyl crotonate gradually as the reaction took place. A reaction rate of 19 gram mols/hour was observed and a 78% yield of gamma formyl butyl butyrate was obtained.

Eramlplc XIII Two hundred grams of diethyl itaconate and two hundred ml. of ethanol containing 5 grams of cobalt carbonyl were charged to a shaker autoclave. Carbon monoxide and hydrogen were pressed in at 140i10 C. and 2100-3000 p. s. i. A` reaction rate of 8.9 gram mols/hour was obtained. Distillation or the product gave 130 "Of i the "three r' possible monoxide -andh drogenV ai-143-165" C. and

senteda o ws.v

Ularly, with acrylate esters*theV a'lf aldehyde'ester The half acid esters are important as intermediates in the preparation of plasticizers, linear polyesters and polyamides.

Gamma formyl ethyl butyrate produced from the ethyl crotonate reaction may be used as the starting point for the preparation of glutaric acid, delta hydroxy and delta amino ethyl valerate, delta valerolactone, 10 carbon dicarboxylic acids, 10 carbon tricarboxylic acids and many others. The delta valerolactone just referred to may be obtained from the hydrogenation of the aldehyde ester followed by the thermal treatment thereof to secure the splitting out of alcohol leaving the lactone. This lactone has particular merit for use in the nail polish remover field and similar solvent purposes.

It is believed from the foregoing that it will be seen that we have provided an improved method for producing useful aldehyde ester compounds.

We claim:

1. The process which comprises reacting ethyl crotonate with carbon monoxide and hydrogen, said reaction being carried out in the presence of a cobalt-containing catalyst, carried in a lower aliphatic alcohol liquid medium, and under temperature and pressure conditions between C. and 1600-35-00 p. s. i., whereby gammaformyl ethyl butyrate is formed.

2. The process which comprises reacting ethyl crotonate with carbon monoxide and hydrogen, said reaction being carried out in the presence of a cobaltfcontaining catalyst carried in butanol and under temperature and pressure conditions between 13D-160 C. and 1600-3500 p. s. i. Whereby gamma-formyl ethyl butyrate is formed.

3. A process for producing aldehyde esters which comprises reacting an ester of an unsaturated acid from the group consisting of lower alkyl crotonates, lower alkyl maleates, lower alkyl sorbates and lower alkyl itaconates with carbon monoxide and hydrogen, said reaction being carried out at a temperature between 130 C. and

160 IC. and a pressure between 160Q-3500 p. s. i. in the presence of a catalyst containing a substantial amount of an eighth group metal capable of forming a metal carbonyl. f

4.A process for producing aldehyde esters which comprises reacting an ester ofthe group consisting of lower alkyl crotonates, lower alkyl maleates, lower alkyl sorbates and'lower'alkyl itaconates with carbon monoxide'and hydrogen, said reaction being carried out' at a temperature between 130 O. and 160? C. and apressure between 1600-3500 p. s. i. in the Apresence of a catalyst containing a substantial amount of an eighth group metal capable of forming a metal carbonyl, said catalyst being further characterized in that it is in an environment essentially comprisedrof a lower aliphaticalcohol.

5; A process for producing aldehyde esters which comprises reacting a lower alk'yl crotonate y 8, withcarbon monoxide `and hydrogen, said reaction beingA carried out at a temperature between 13o-160 C; and a pressureV between i600-3500 p. s. i. in the presence of a catalyst containing a substantial amount of an eighth group metal capable of forming a metal carbonyl, said catalyst being. further characterizedin that it is in an environment essentially/*comprised of a lower aliphaticfalcohol. 1 v.

V.HUGH J. HAGEMEYEB, Ja.

DAVID C. `I-l'ULL.

vREFERENCES CI'1AED` The following references are of record in the le of this pa-tent:

UNITED STATES PATENTS Number A Name n "Date 2,437,600 Y, Gresham .Y.. Mar.9 ,1948 

1. THE PROCESS WHICH COMPRISES REACTING ETHYL CROTONATE WITH CARBON MONOXIDE AND HYDROGEN, SAID REACTION BEING CARRIED OUT IN THE PRESENCE OF A COBALT-CONTAINING CATALYST, CARRIED IN A LOWER ALIPHATIC ALCOHOL LIQUID MEDIUM, AND UNDER TEMPERATURE AND PRESURE CONDITIONS BETWEEN 103106* C. AND 1600-3500 P. S. I., WHEREBY GAMMAFORMYL ETHYL BUTYRATE IS FORMED. 